Method for coating paper



Patented Jan. 18, 1 944 a nm'rnon'ron COATING PAPER.

Otto Kress and Charles Johnson, Appleton, Wis., assiznors to The Institute of Paper Chemistry, Appleton, Wis, a corporation of Wisconsin No Drawing.

Application December 13, 1939, Serial N0. 308,944

' 2.Cla ims. (01. 106-142) The present invention relates to compositions adaptable for use in the paper art and more par ticularly to aqueous emulsions containing non-- volatile solid material and volatile water-insoluble liquid material and the use of the same in the manufacture of improved paper.

.' The principal object of the present invention is to provide compositions for use. in the manufacture of improved paper.

Other objects of the present invention will be apparent as the description hereinafter proceeds.

' We have discoveredthat paper of improved brightness and increased opacity can be readily prepared by first treating a paper web or sheet with an aqueous emulsion containing as essential ingredients 9. non-volatile solid material and a volatile water-insolubleliquid, and thereafter subjecting the treated web to a heat treatment in order to remove the volatile liquid. The followingpreferred procedure will serve to illustrate' the preparation of an emulsion of and for usein the present invention.

About 40 pounds of a water-insoluble, alkalisoluble protein, such for example as an animal casein such as milk protein or a vegetable casein such as soya bean protein, is first stirred into about 160 poimd of water at a temperature of approximately 140 F. As soon as the protein is wetted about 1.2 pounds of caustic soda dissolved in ii) pounds of water is added to the'protein dispersion and the mixture subjected to mild agi tation until solution of the protein is obtained.

About 7.5 pounds of an emulsifying agent, e. g.

ammonium-oieate, is next added to the protein solution and the resulting mixture subjected to an additional mixing for a short period, e. 15

speedwl ofmixerknowninthetradeasthe mayoperateataspeed Lllhtnin mixer, which varringn'omdoomnmtolvwnnm. After the kerosene or like material has been thorouahly emulsified with the protein preferably throughtheuse ofsoap or'other emulslfyin: amt. the emulsion is diluted with water tothe desired concentration and is ready for use.

The of the pr sen invention P 'Mformmrlaasdescrlbedabovesnomdbe applied to the formed web or paper sheet and are not suitable for use in the beater prior to web formation. The emulsions may be applied in the usual manner at the size press or applied 'by spraying, or by any other of the various proceto volatilize or evaporate the water-insoluble oily quid.

The method outlined above provides a satisfactory and relatively cheap means for brighten-' ing and opacifying the finished sheet and for increasing the uniformity of formation, as well as the oil resistance and strength or the finished sheet. It is customary to secure opacity by the addition at the beater of-so-called fillers, which are-mineral pigments; the addition of such fillers will brighten the sheet and increase its opacity, but at the same time will tend to reduce the strength and oil resistance of the sheet. Moreover, unless very expensive fillers such as titanium v dioxide are used, a very large percentage of filler Such a treatment is expensive and decidedly in-.

must be incorporated in the sheet; this, in turn, very decidedly reduces the strength of the sheet, increases its weight unduly, and reduces its oil resistance. We do not intend in this application to come into conflict with what i normally known as coated paper, which is made by using a dispersionof starch, casein, glue etc. into which'is admixed a pigment or filler, and the mixture is then applied as a surface coating to th sheet.

creases the weight of the sheet, as a relatively heavy coating must be applied to secure the desiredopacity.

The solid material or protein remaining on the paper (which is not dependent on acidity for. the breaking of the emulsion) does not form a continuous film, but is in very fine, submicroscopic'particle size and gives the effect of producinga sheet of more uniform formation. The

light striking the small particles is refracted producing the unique increase in opaoity,azi improvement not obtainable by applying, for ex ample, casein dissolved in-alkali or other solvent.

No appreciable increase in opacity or'brlghtness is secured when a material, such as protein, is

applied by itself in accordance with prior pracdoes and forms continuous films.

, alpha protein are examples.

.vention. The emulsions should The paper treated in accordance with the present invention possesses a very decided advantage in that it is relatively resistant to penetration of oils, although the surface of the paper is not disturbed by the treatment insofar as its receptivity toward Ordinary writing inks is concerned. These characteristics, i. e., resistance to' oil penetration and high surface ink receptivity, make the paper treated with the emulsions of the present invention of special interest for certain types of printing papers in which excessive oil penetration is not desired. The paperstreated in accordance with the present invention in addition, are more readily erasedr -especlally 'in the case of typewriter ink. This \is believed to be due to the fact that the ink does not P trate into the body of the sheet but lies more upon the surface. It will be understood, however, that the present invention is not limited by any theoretical explanations discussed herein.

The non-volatile solid materials suitable for 2,sao,7o7

aqueous emulsions; (2). an inert, oily, water-- insoluble volatile liquid; and (8) a non-volatile solid material which separates from the emulsion in very fine particle form, i. e. does not produce a continuous film, when the water and oily-liquid are removed by evaporation or volatilization. The drying operation breaks the emulsion, and the evaporation of the emulsified oily material is responsible for producing the minute -orsubmicroscopic particles of non-volatile brightening material and opacifying agent on the surface of the treated paper. v

It will be understood by those skilled in the art that our invention is not limited to the temperause in the present invention should be in aqueous solution and in the case of the proteins (which are in alkaline dispersion) should be water-insoluble and alkali-soluble, and preferably of the casein type ofwhlch milk casein and soya bean caustic soda used in the aboveillustrative example, may be replaced in whole or in part by other alkaline materials, such 'as ammonia, sodium carbonate, borax, disodium phosphate, so dium, silicate, etc., or any of the other alkalies normally employed for the purpose of cutting or dissolving water-insoluble proteins, such as casein.

The kerosene used in the above illustrative example may also be replaced in whole or in part by other inert, organic liquids. e. g. the hydrocarbons, or mixtures of the same which are not miscible with water under normal conditions.

The preferred oil, which should be water-white and must, leave no odorous residues after drying, should have a flash point ofabout 115 to 150 F.

. and a fire point of approximately 130 to 180 F.

The oil should not contain heavy or high boiling point residues which cannot be driven from the treated sheet by the temperature employed The alkali, such as Y has been found satisfactory turesand proportions of the various ingredients employed in our preferred process described above. For example, our investigations have shown that a 3:1 to 1:3 volatile water-insoluble, organic liquid to solid material ratio may be employed. The use of a 4:1 or even 5:1 organic liquid to solid material ratio may also be em-.

ployed althoush theuse of such large amounts of emulsifiedorganic liquid is ordinarily not neces- "sary and is avoided in commercial practice.

When using protein a 3:1 to 1:3 organic liquid to protein ratio has been found most desirable i with a 3: 1 to 1:1'oily material to" casein protein ratio being preferred. The temperature of the dispersion on addition of the organic liquid should be substantially below the boiling point 1 of the organic liquid. A temperature'of about 120 F. (as illustrated in the preferred example) when emulsifying kerosene. I

It will be understood by those skilled in the art that the concentration of the'emulsion and/or the amount applied to the paper web will govern either in drying on steam cylinders or by hot air.

drying. Naturally, oilsoi' lower or higher flash and fire point than indicated above could be employed, provided precautions were taken for the removal of all of the oily residues which might be present in the oil, as such'oily residues will tend to lubricate the fibers and thereby reduce the strength characteristics of the finished sheet.

Although we prefer to employ an emulsifying of the nature of the sulfonated oils, triethan'olamine, etc, as an aid in the formation of the emulsion, the addition of or use of an emulsifying agent is not essential. We have found, for example, that a satisfactory product can be made agent such as ammonium oleate, or other agents by omitting the emulsifying agent entirely and by depending upon, for example, the alkaline solution of casein and the agitation for the proper liquid oily material.

It will be understood that the compositions or emulsification of the water-insoluble. organic .and opacifying'paper which comp the results obtained. The optimum concentrations (ordinarihr from 20 to 45 per cent) and amounts ofemulsion to be used (which may vary with different types of paper) may be determined by preliminary laboratory experiment.

It will likewise be understood by those skilled in the art that the present invention is not limited to the above illustrative examples. 'All modiflcations of the present invention are intended to be covered by the claims annexed hereto.

We claim:

1-. In the paper art, the method or brightening and opacifying paper which comprises treating a casein, and thereafter subjecting the treated web to a drying treatment in order to evaporate the liquid material 'of said emulsion including the hydrocarbon liquid and leave the casein on the surface of said web in extremely fine particle 2. In the paper art, the method of brightening e b v rises treating a proformed paper web with an aqueous emulsion consisting essentially-of kerosene with aflash point of about -150 E, ammonium oleate and an alkaline dispersion ofcas'ein, and there after subiecting the treated .web to, a drying treatment in order to evaporate the liquid material of said emulsion including the kerosene and leave the casein on the surface of said web in submicroscopic particle size.

. CHARLIBEJOHNBON.

CERTIFICATE OF CORRECTION. v Patent No. 2, 59,707. January 18, one KRESS, ET AL.

It is hereby certified that error appears in the printed specification of the above numb ered patent requiring correction as follows: Page 2, first column,'line 51-52, for *fsodium, il read --sodium ai1ioat,eand that the said Letters Patent dfould be read with this correction therein that the sane may conform to the record of the cal-Be in the Patent office Signed end-sealed this 1l4.th day of MercH, A. 1:. 191m.

Leslie Frazer (Seal) Acting Commissioner of Patents.- 

